Production of hydrocarbons



July 25, '1939. H ET A 2,167,004 v PRODUCTION OF Hi DROCARBONS Filed Deb. 16, 1936 M/zthehn Michael Ml fgargg Jaeckh INVENTORS ux Mksflk THEIR A'ITORNEYS and Jul 2'5, 1939 UNITED STATE monUc'noN or mnocannons Mathias Pier, Heidelberg, Wilhelm Michael, cudwigshaten on the Rhine, and -Wol1gang Jaeckh, Heidelberg, Germany, asslgnors to I. G. Farbenindustrie Aktiengcsellschait, Frankforton-the-Main, Germany I Application December 16, 1936, Serial No. 116,124

In Germany D 4 Claims.

This invention relates to the production of hydrocarbons, in particular those containing at least two carbon atoms in the molecule, by the interaction of carbon monoxide with hydrogen.

ecember 20, 1935 of catalytic substances, such as for example those containing metals of the iron group, such as iron or nickel, may be employed. Precipitates of catalytic substances on pumice stone or pieces, nets or .In the conversion of carbon monoxide by means balls of metal, clay, procelain or glass may also 5 of hydrogen into liquid, solid and/or gaseous be used, hydrocarbons it may happen that products of The liquid medium used according to this inhigh molecular weight, in particular paraflin vention may be passed in the same direction as waxes, formed during the reaction settle on the the gases or in counter-current thereto. Bull;-

catalyst and impair its activity. The strong evoable liquids are alcohols, hydrocarbons and other 10 lution of heat occurring in this reaction readily liquids which do not injure the catalysts and leads to thermal congestion in the catalysts, which remain liquid under the working condiwhereby it is diflicult or quite impossible without tions or are only partly vaporized during the coolthe use of special measures to maintain the deing process. As liquids suitable for the reduction sired reaction temperature, such as a great subof carbon monoxide are especially those in which 15 division of the reaction chamber in order to leadthe products of high molecular weight formedaway the heat. during the reaction are readily dissolved or sus- We have now found that the said conversion pended, in particular organic solvents, such as of carbon monoxide and hydrogen into hydrocarmiddle oils, heavy oils, parafin oils and anthrag0 bons, in particular those containing at least two cene oils, and in particular liquid substances. carbon atoms in the molecule, which is very senformed during the reaction itself, 1. e. the charsitive as regards the temperature to be mainacteristic oil. (it this characteristic oil, it is tained, can be carried out very smoothly without preferable to use fractions of which at least a great trouble or difilculties as regards apparatus considerable portion remains liquid under the by continuously or periodically trickling the reaction conditions. Similarly when using .for- 25 rigidly arranged catalyst with a liquid during eign liquids, at least a part of the same should the conversion whereby the catalyst is mainremain liquid under the reaction conditions. The tained at a desired temperature. when working amount of liquid medium is preferably selectedin this manner theactivlty oi the catalyst does so that there is always a thin layer of liquid so not subside during the reaction. Since the reacpresent on the surface of the catalyst, In some so tion is to be carried out in the gas phase the forcases it may be advantageous temporarily to inmation of .a liquid level in the reaction chamber terrupt the trickling, especially when a temposhould be avoided. By the said trickling the setrary increase in. temperature at the catalyst is tling 01 products of high molecular weight on the desired. The liquid is advantageously pumped catalyst is prevented because any products of in circulation, if desired while interposing heat- 35 high molecular weight deposited on the catalyst exchangers.- The operation according to the may be dissolved on again and furthermore a present invention may be effected at any desired cooling of the catalyst takes placeso that it is pressures. For example a slight excess pressure, possible to arrange the catalyst in tubes of any such as 2, 3, ,5 or 10 atmospheres, orhigher preswidth. Since the liquid medium trickles down sures, such as 50, 100 atmospheres or more, may 40 at the surface of the catalyst and cover the latter be used. Atmospheric pressure or reduced presonly in a thin layer, the gases to be brought into sure may also be employed. l a

reaction can-readily contact with the catalyst It has also been Sound to be advantageous to because the distance which the gases-have to withdraw the liquid medium together with the travel through the liquid is only very small. This reaction products tromthe reaction chamber at is of considerable advantage as compared with I the lower end thereof. A separation oi" the liqworking while wholly or partly filling the reac: uidmedium from the reactlonproducts may-be tion chamber with liquid in which case thegases effected by known methods, as tor. example by cannot contact so readily with the catalyst. strong cooling, distillation or the use of selective I As catalysts suitable for the said conversion solvents, I a 5 may be mentioned any substances catalytically 1 Whenpasslngtheliquid medium in a cycle over romoting this conversion which are rlgidly arthe catalyst the liquid and high molecular reacranged either in the form of pieces or precipition products absorbed by the liquid medium maytated on carriers, advantageously metallic carbe removed'th'erefl'om continuously or at certaingrlerarorenmplepleceaflnsnballsornets lntervaliottime.

The conversion is carried out at the usual temperatures, preferably above 150 C. and advantageously between 200 and 450 C.

The composition of the initial gases may be asusual.

The iollowing example is given with respect to the accompanying drawing which illustrates in a diagrammatic manner an elevation in section of an example of apparatus suitable according to this invention, and will further illustrate how this invention may be carried out in practice but 'the invention is not restricted to this example or to the particular example of apparatus shown.

Example A mixture of carbon monoxide and hydrogen isled through a pipe linto the upper part of a reaction chamber i charged with a rigidly ar ranged catalyst consisting for example of iron with 5 per cent 01' aluminium oxide. Paraflln oil is introduced throughthe pipe 3, the liquid being ')distributed uniformly over the cross-section of the catalyst space by the nozzle 4. The catalyst, which is arranged in the reaction chamber in the form 01' pieces, is thus uniformly trickled by the paraflin oil. No liquid level is maintained in the catalyst chamber so that the spaces between the pieces oi catalyst are almost entirely filled by the reaction gases. The mixture of parailln oil and liquid and gaseous reaction products flows downwards into a cooled separating vessel 5 in which the separation of the liquid from gases takes place and in which a liquid level 8 is maintained. The gaseous portion, consisting mainly of unconverted initial gas, is withdrawn through the pipe 6 and may bei'urther reacted in a second reaction chamber or returned to the same reaction chamber for further reaction. The liquid portion is removed through the pipe I.

What we claim is:

1. A process for carrying out the conversion of carbon monoxide with hydrogen for the production of hydrocarbons in the presence of a rigidly arranged catalyst which comprises passing the conversion as remain at least in part liquid under the operation condition and trickling them as liquid medium over the catalyst."

i. A process for carrying out the conversion or carbon monoxide withhydrogen'for the production of hydrocarbons in the presence of a rigidly arranged catalyst which comprises passing the. a

said carbon monoxide and hydrogen at a reacting temperature over such catalyst and simultaneously trickling over the catalyst a petroleum 'oil' so which is at least. partly liquid under the conditions employed, while avoiding the formation of a liquid level in the catalyst space.

' MATHIAS PIER.

WILHELM MICHAEL. '35

WOLFGANG JAECKH. 

